U.S. patent application number 10/023822 was filed with the patent office on 2002-09-19 for remover composition.
Invention is credited to Ichiki, Naoki.
Application Number | 20020130298 10/023822 |
Document ID | / |
Family ID | 18863489 |
Filed Date | 2002-09-19 |
United States Patent
Application |
20020130298 |
Kind Code |
A1 |
Ichiki, Naoki |
September 19, 2002 |
Remover composition
Abstract
A remover composition comprising (a) 100 parts by weight of a
composition obtained by adding a cyclic urea compound to water,
water-soluble organic solvent, or a mixture of water and
water-soluble organic solvent so that the concentration of the
cyclic urea compound is from 1 to 90% by weight, wherein the cyclic
urea compound is represented by the following general formula (I):
1 wherein, R.sub.1 and R.sub.2each independently represent alkyl
group which may be substituted, hydrogen atom, hydroxyl group, or
carboxyl group, Z represents oxygen atom or sulfur atom, (b) 0.1 to
150 parts by weight of an organic amine, and (c) 0.001 to 100 parts
by weight of a salt of an amine with an acid.
Inventors: |
Ichiki, Naoki; (Tsukuba-shi,
JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
18863489 |
Appl. No.: |
10/023822 |
Filed: |
December 21, 2001 |
Current U.S.
Class: |
252/79.1 ;
257/E21.228; 257/E21.252; 257/E21.255 |
Current CPC
Class: |
H01L 21/02063 20130101;
G03F 7/425 20130101; H01L 21/02052 20130101; H01L 21/31116
20130101; H01L 21/31133 20130101; C09K 13/00 20130101 |
Class at
Publication: |
252/79.1 |
International
Class: |
C09K 013/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 27, 2000 |
JP |
2000-398547 |
Claims
What is claimed is:
1. A remover composition comprising (a) 100 parts by weight of a
composition obtained by adding a cyclic urea compound to water,
water-soluble organic solvent, or a mixture of water and
water-soluble organic solvent so that the concentration of the
cyclic urea compound is from 1 to 90% by weight, wherein the cyclic
urea compound is represented by the following general formula (I):
3 wherein, R.sub.1 and R.sub.2each independently represent alkyl
group which may be substituted, hydrogen atom, hydroxyl group, or
carboxyl group, Z represents oxygen atom or sulfur atom, (b) 0.1 to
150 parts by weight of an organic amine, and (c) 0.001 to 100 parts
by weight of a salt of an amine with an acid.
2. The remover composition according to claim 1, wherein the
organic amine is selected from the group consisting of alkanolamine
and alkylammonium hydroxide.
3. The remover composition according to claim 1, wherein the amine
is selected from the group consisting of alkanolamine,
alkylammonium hydroxide and hydroxylamine, and the acid is selected
from the group consisting of hydrochloric acid, sulfuric acid,
nitric acid and carboxylic acid.
4. A remover composition according to claim 1 further comprising an
additive.
5. The remover composition according to claim 4, wherein the
additive is selected from the group consisting of an aromatic
hydroxy compound and a triazole compound.
6. A process for removing a photoresist with the remover
composition according to claim 1.
7. A process for removing a residue of a semiconductor element
generated in semiconductor treatment with the remover composition
according to claim 1.
8. The process according to claim 7, wherein the semiconductor
treatment is dry etching treatment.
9. A remover composition comprising (a) 100 parts by weight of a
composition containing a cyclic urea compound in water,
water-soluble organic solvent, or a mixture of water and
water-soluble organic solvent so that the concentration of the
cyclic urea compound is from 1 to 90% by weight, wherein the cyclic
urea compound ie represented by the following general formula (I):
4 wherein, R.sub.1 and R.sub.2 each independently represent alkyl
group which may be substituted, hydrogen atom, hydroxyl group, or
carboxyl group, Z represents an oxygen atom or sulfur atom, (b) 0.1
to 150 parts by weight of an organic amine, and (c) 0.001 to 100
parts by weight of a salt of an amine with an acid.
10. The remover composition according to claim 9, wherein the
organic amine is selected from the group consisting of alkanolamine
and alkylammonium hydroxide.
11. The remover composition according to claim 9, wherein the amine
is selected from the group consisting of alkanolamine,
alkylammonium hydroxide and hydroxylamine, and the acid is selected
from the group consisting of hydrochloric acid, sulfuric acid,
nitric acid and carboxylic acid.
12. The remover composition according to claim 9 further comprising
an additive.
13. The remover composition according to claim 12, wherein the
additive is selected from the group consisting of an aromatic
hydroxy compound and a triazole compound.
14. A process for removing a photoresist with the remover
composition according to claim 9.
15. A process for removing a residue of a semiconductor element
generated in semiconductor treatment with the remover composition
according to claim 9.
16. The process according to claim 15, wherein the semiconductor
treatment is dry etching treatment.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a remover composition. More
particularly, the present invention relates to a remover
composition which removes a photoresist or residue generated in
manufacturing a semiconductor.
[0003] 2. Description of Related Art
[0004] Recently, formation of finer patterns of high precision is
required due to increased concentration of integrated circuits,
therefore, dry etching methods using a halogen-based gas are often
used instead of conventional chemical etching methods, and further,
ashing by oxygen plasma, ion injection and the like are
conducted.
[0005] In such dry etching methods, ashing treatment and the like,
a photoresist film is oxidized by a halogen-based etching gas,
oxygen and the like, and changes from a film showing an organic
property to a film showing an inorganic property, and changes into
a film of poor solubility by an ion injection treatment.
[0006] Remover compositions are used for removing, photoresists and
residues after dry etching remaining on the surface parts of wiring
layers or insulation film layers, side wall parts of wiring layers
or Via Holes, or bottom part of Via Holes, generated in forming
wiring layers of a conductive metal and Via Hole.
[0007] As the remover composition, there is used, conventionally, a
mixture of an organic alkali, inorganic alkali, organic acid,
inorganic acid and polar organic solvent, or an aqueous solution
thereof, and for example, JP-A No. 59-49539 discloses a remover
composed of a 2-pyrrolidine compound and a dialkylsulfone compound,
JP-A No. 4-350660 discloses a remover composed of
1,3-dimethyl-2-imidazolydinone and dimethylsulfoxide, JP-B No.
6-12455 discloses a remover composed of an alkanolamine, sulfone
compound and glycol monoalkyl ether, and Japanese Patent No.
3048207 discloses a remover composed of (a) a nucleophilic amine
such as hydroxylamine, hydrazine and the like, (b) an organic
solvent, (c) a reducing agent such as catechol and the like, and
(d) water, and the like.
[0008] With progress of size reduction of semiconductor elements, a
problem of corrosion of a metal film used in a wiring layer also
occurs in a process of removing a resist and a process of removing
a residue after dry etching. When a metal film used in a wiring
layer is corroded, resistance increases, leading to occurrence of
problems such as increase in consumption power, heat generation
from a semiconductor element, and the like.
[0009] However, the above-mentioned conventional releasing
compositions have problems that ability of removing a resist and, a
residue after dry etching is not sufficient, and corrosion of a
metal film used in a wiring layer occurs, and the like.
[0010] Therefore, there is a desire for development of a remover
composition having higher removing ability and does not easily
cause corrosion of a metal film used in a wiring layer.
SUMMARY OF THE INVENTION
[0011] An object of the present invention is to solve the
above-mentioned problems, and to provide a remover composition
manifesting an extremely low corrosion property against materials
such as an insulation film, metal film and the like constituting a
semiconductor, and having a high ability of removing a photoresist
and a residue generated in treating a semiconductor.
[0012] The present inventors have intensively studied a remover
composition having no problems described above, and resultantly,
found that a remover composition obtained by adding a cyclic urea
compound having a specific structure manifests an extremely low
corrosion property against materials such as an insulation film,
metal film and the like, and has a high ability of removing a
photoresist and a residue generated in treating a semiconductor
element, and have completed the present invention.
[0013] Namely, the present invention relates to a remover
composition comprising
[0014] (a) 100 parts by weight of a composition obtained by adding
a cyclic urea compound to water, water-soluble organic solvent, or
a mixture of water and water-soluble organic solvent so that the
concentration of the cyclic urea compound is from 1 to 90% by
weight,
[0015] wherein the cyclic urea compound is represented by the
following general formula (I): 2
[0016] wherein, R.sub.1 and R.sub.2 each independently represent
alkyl group which may be substituted, hydrogen atom, hydroxyl
group, or carboxyl group, Z represents oxygen atom or sulfur
atom,
[0017] (b) 0.1 to 150 parts by weight of an organic amine, and
[0018] (c) 0.001 to 100 parts by weight of a salt of an amine with
an acid.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] The present invention will be explained in detail below.
[0020] The remover composition of the present invention is
characterized in that it is obtained by addition of a cyclic urea
compound of the general formula (I) so that the concentration
thereof is from 1 to 90% by weight, or it contains a cyclic urea
compound of the general formula (I) so that the concentration
thereof is from 1 to 90% by weight. The addition amount or content
of the cyclic urea compound is preferably from 10 to 60% by weight,
particularly preferably from 10 to 40% by weight.
[0021] Specifically, the remover composition of the present
invention is prepared by adding the above-mentioned cyclic urea
compound to water and/or organic solvent, or contains the
above-mentioned cyclic urea compound in water and/or organic
solvent.
[0022] Namely, the remover composition of the present invention is
characterized in that it is obtained by adding of a cyclic urea
compound of the general formula (I) to water and/or water-soluble
organic solvent so that the concentration thereof is from 1 to 90%
by weight, or it contains a cyclic urea compound of the general
formula (I) in water and/or water-soluble organic solvent so that
the concentration thereof is from 1 to 90% by weight. The addition
amount or content of the cyclic urea compound is preferably from 10
to 60% by weight, particularly preferably from 10 to 40% by
weight.
[0023] When the concentration is less than 1% by weight, releasing
property for a photoresist and etching residue is insufficient. On
the other hand, when the concentration is over 90% by weight,
releasing property for an etching residue is insufficient.
[0024] In a cyclic urea compound of the general formula (I) in the
present invention, R.sub.1 and R.sub.2 each independently represent
a hydrogen atom, hydroxyl group, carboxyl group or alkyl group
optionally substituted. Z represents an oxygen atom or sulfur
atom.
[0025] When R.sub.1 and R.sub.2 represent an alkyl group optionally
substituted, groups of the following general formula (II):
--(CH.sub.2).sub.n--X (II)
[0026] (wherein, n represents an integer of 1 or more. X represents
a hydrogen atom, hydroxyl group, methoxy group or ethoxy group.)
are listed for R.sub.1 and R.sub.2 each independently.
[0027] From the standpoint of sufficient ability for removing a
photoresist and an etching residue, preferable R.sub.1 and R.sub.2
represent a hydrogen atom or an alkyl group optionally substituted
of the general formula (II), n represents preferably 1 to 4,
particularly preferably 1 to 2. Further, in view of raw material
circumstances together, it is preferable that
R.sub.1.dbd.R.sub.2.
[0028] Examples of the cyclic urea compound of the general formula
(I) include 4,5-dihydroxy-2-imidazolidinone,
4,5-dihydroxy-1,3-dimethyl-2-imi- dazolidinone,
4,5-dihydroxy-1,3-bis(hydroxymethyl)-2-imidazolidinone,
4,5-dihydroxy-1,3-bis(methoxymethyl)-2-imidazolidinone, and the
like.
[0029] Examples of the organic solvent in the present invention
include alcohols such as methanol, ethanol, n-propyl alcohol,
isopropyl alcohol, n-butanol, t-butyl alcohol, pentanol, ethylene
glycol, glycerin and the like; amides such as N-methylformamide,
N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone and the like; lactones such as
.gamma.-butyrolactone and the like; esters such as propyl acetate,
butyl acetate, butyl propionate, ethyl butyrate, butyl butryrate,
methyl lactate, ethyl lactate and the like; ketones such as
acetone, methyl ethyl ketone, acetylacetone, methyl butyl ketone,
3-pentanone, 2-heptanone and the like; ethers such as diethyl
ether, dipropyl ether, dibutyl ether, oxirane, dioxane and the
like; glycol monoethers such as ethylene glycol monomethyl ether,
ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
diethylene glycol monomethyl ether, diethylene glycol monoethyl
ether, diethylene glycol monobutyl ether, triethylene glycol
monomethyl ether and the like; furan such as tetrahydrofuran,
furaldehyde, tetrahydrofurfurylalchol and the like; sulfolanes such
as sulfolane and the like; sulfoxide such as dimethylsulfoxide and
the like; urea compounds such as dimethylimidazolidinone and the
like, hydrocarbons such as pentane, hexane, heptane,cyclohexane and
the like, and other solvents. Among them, water-soluble organic
solvents having a solubility in water of 8% or more are
preferable.
[0030] Examples of the water-soluble organic solvent in the present
invention include alcohols such as methanol, ethanol, n-propyl
alcohol, isopropyl alcohol, ethylene glycol, glycerin and the like;
amides such as N-methylformamide, N,N-dimethylformamide,
N,N-dimethylacetamide, N-methyl-2-pyrrolidone and the like;
lactones such as .gamma.-butyrolactone and the like; esters such as
methyl lactate, ethyl lactate and the like; ketones such as
acetone, methyl ethyl ketone, acetylacetone and the like; ethers
such as ethylene glycol monomethyl ether, ethylene glycol monoethyl
ether, diethylene glycol monomethyl ether, diethylene glycol
monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol
monobutyl ether, triethylene glycol monomethyl ether and the like;
furan such as tetrahydrofuran, furaldehyde,
tetrahydrofurfurylalchol and the like; sulfolanes such as sulfolane
and the like; sulfoxide such as dimethylsulfoxide and the like;
urea compounds such as dimethylimidazolidinone and the like, and
other solvents. Further preferably, N-methyl-2-pyrrolidone,
methanol, dimethylsulfoxide and the like are listed. These
water-soluble organic solvents may be used alone or in combination
of two or more.
[0031] It is preferable that the remover composition of the present
invention further contains organic amines. Regarding preferable
ratio thereof, the remover composition comprises 100 parts by
weight of a remover composition which is prepared by adding 1 to 90
weight % of a cyclic urea compound of the general formula (I) to
water and/or water-soluble organic solvent, or contains this cyclic
urea compound in water and/or water-soluble organic solvent, and
0.1 to 150 parts by weight, further preferably 1.0 to 100 parts by
weight, particularly preferably 5.0 to 50 parts by weight of
organic amines.
[0032] When the ratio of the organic amines is over 150 parts by
weight, corrosion of an insulation film or conductive metal on a
substrate may occur, and when less than 0.1 part by weight,
releasing property may be insufficient for a resist and an etching
residue.
[0033] The organic amines are selected from the group consisting of
alkanolamines and alkylammonium hydroxides. These amines may be
used alone or in combination of two or more. As the above-mentioned
alkanolamine, monoethanolamine, diethanolamine, triethanolamine,
2-(2-aminoethoxy)ethanol and the like are listed. As the
above-mentioned alkylammonium hydroxide, tetramethylammonium
hydroxide, tetraethylammonium hydroxide and the like are listed.
These organic amines may be used alone or in combination of two or
more.
[0034] The remover composition of the present invention preferably
contains a salt of amines with an acid. Further, the remover
composition of the present invention preferably contains a salt of
amines with an acid, in addition to the above-mentioned organic
amines.
[0035] Specifically, the remover composition of the present
invention comprises 100 parts by weight of the above-mentioned
remover composition and 0.001 to 100 parts by weight, preferably
0.1 to 50 parts by weight, particularly preferably 1.0 to 25 parts
by weight of additives. The addition amount of the above-mentioned
additives is also applied to a remover composition containing
organic amines added.
[0036] In the salt of amines with an acid, the amines are selected
from alkanolamines and alkylammonium hydroxides, and
hydroxylamines, and the acid is selected from the group consisting
of hydrochloric acid, nitric acid, sulfuric acid, carboxylic acids.
A salt can be obtained by combining these amines with an acid. As
the above-mentioned alkanolamine, monoethanolamine, diethanolamine,
triethanolamine, 2-(2-aminoethoxy)ethanol and the like are listed.
As the above-mentioned alkylammonium hydroxide, hydromethylammonium
hydroxide, tetraethylammonium hydroxide and the like are listed. As
the above-mentioned hydroxylamines, hydroxylamine,
N,N-diethylhydroxylamine and the like are listed. As the carboxylic
acids, formic acid, acetic acid, oxalic acid and the like are
listed. These salts of amines with an acid may be used alone or in
combination of two or more.
[0037] Regarding the salt of amines with an acid, those manifesting
particularly an effect of releasing a photoresist and etching
residue can be used, and for example, monoethanolamine
hydrochlorides, hydroxylamine hydrochlorides, hydroxylamine
sulfates and the like are listed. These may be used alone or in
combination of two or more. When the concentration of the additive
is over 100 parts by weight, solubility may decrease or corrosion
of a metal film on a substrate may occur, when less than 0.001 part
by weight, an ability of removing an etching residue may
decrease.
[0038] The remover composition of the present invention preferably
contains an additive. Further, the remover composition of the
present invention preferably contains an additive in addition to
the above-mentioned organic amines.
[0039] Regarding specific ratios, the remover compositions of the
present invention comprising 100 parts by weight of the
above-mentioned remover composition and 0.001 to 100 parts by
weight, preferably 0.1 to 50 parts by weight, particularly
preferably 1.0 to 25 parts by weigh of an additive, are listed. The
addition amount of the above-mentioned additive is applied also to
a remover composition containing organic amines added.
[0040] As the additive, there can be used reducing agents and
chelating agents, particularly, those having an effect as a
corrosion inhibiting agent for a metal can be used, and examples
thereof include aromatic hydroxy compounds, triazole compounds and
the like. These may be used alone or in combination of two or more.
When the concentration of the additive is over 100 parts by weight,
the additive may remain on a substrate after treatment with a
remover, and when less than 0.001 part by weight, corrosion of a
metal film on a substrate may occur.
[0041] As the above-mentioned aromatic hydroxy compound,
hydroquinone, catechol, resorcinol, pyrogallol and the like are
listed, and among them, catechol is preferable. As the
above-mentioned triazole compound, benzotriazole,
carboxybenzotriazole, 1-hydroxybenzotriazole, 3-aminotriazole and
the like are listed, and of them, benzotriazole is preferable. As
the other additives, polyethyleneimide, thioglycol and the like are
listed. These compounds may be used alone or in combination of two
or more.
[0042] The remover composition of the present invention manifest
extremely low corrosion property for materials such as an
insulation film and metal film (film made of aluminum, tungsten,
copper, platinum and the like) and the like constituting a
semiconductor element, and the remover composition is particularly
suitable for copper and aluminum, among them.
[0043] A cyclic urea compound of the general formula (I) can be
obtained by reacting the corresponding urea compound or thiourea
compound with glyoxal by a usual method, or introducing an
N-substituent into a reaction product of urea or thiourea with
glyoxal (R.sub.1.dbd.R.sub.2.db- d.H in the general formula (I)) by
a usual method.
[0044] For obtaining the remover composition of the present
invention, the above-mentioned compounds may be mixed in give
amounts. The mixing method is not particularly restricted, and
various known methods can be applied.
[0045] The remover composition of the present invention is
excellent in an ability of removing a photoresist and a residue
generated in dry etching treatment, can suppress corrosion tendency
of materials such as an insulation film, metal film and the like
constituting a semiconductor element, and is suitably used in a
process of washing semiconductor elements such as an LSI element,
liquid crystal panel element and the like.
[0046] The method of removing a photoresist of the present
invention is characterized in that it removes a photoresist by
using the remover composition of the present invention, in a
process of producing a semiconductor.
[0047] Further, the method of removing a residue of a semiconductor
element of the present invention is characterized in that it
removes a residue generated in semiconductor treatment,
particularly in dry etching treatment, by using the remover
composition of the present invention, in a process of producing a
semiconductor.
[0048] Here, the residue means ashing residue, etching residue and
the like.
[0049] Specifically, in a method of removing a resist and etching
residue by using the remover composition of the present invention,
an LSI element and liquid crystal panel element may be
advantageously be washed with the remover composition of the
present invention using an immersion method or spray washing method
at temperatures from 10 to 100.degree. C.
EXAMPLES
[0050] The following example illustrate the present invention
further in detail below, but the scope of the invention is not
restricted by this example.
Example 1-3, Comparative Example 1
[0051] In a substrate comprising a silicon wafer, a titanium
nitride (TiN) layer as the first layer on the wafer, an aluminum
layer as the second layer on the first layer, and an insulation
film (silicon oxide (SiO.sub.2)) layer as the third layer on the
second layer, via holes were formed by dry etching using a resist
film as a mask, subsequently, the resist film was removed by ashing
using oxygen plasma. Residues which cannot be removed by oxygen
plasma were present on the upper part of the insulation film, the
wall part of the via hole and the bottom part of the via hole.
[0052] This wafer was immersed in a remover composition shown in
Table 1 or Table 3 under treatment conditions shown in Table 2 or
Table 4, then, rinsed with ultrapure water and dried, and observed
by a scanning electron microscope (SEM). The property of releasing
residues and property of corroding of a copper layer were evaluated
and the results are shown in Table 2 or Table 4. The evaluation
criteria in SEM observation are as described below.
Releasing Property
[0053] .circleincircle.: complete removal
[0054] .DELTA.: partial remaining is recognized
[0055] X: most part remain
Corrosion Property
[0056] .circleincircle.: corrosion is not recognized at all
[0057] .DELTA.: partial corrosion is recognized
[0058] X: severe corrosion is recognized
1 TABLE 1 Example Comparative 1 example 1 Compound of the formula
part by weight 12.0 12.0 (I): A Water part by weight 18.0 18.0
Water-soluble organic part by weight 39.0 39.0 solvent: EGB Organic
amines: MEA part by weight 20.0 20.0 Additive: catechol part by
weight 10.0 11.0 BTA part by weight 1.0 1.0 HAS part by weight 3.0
--
[0059] A: 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone
[0060] MEA: monoethanolamine
[0061] EGB: ethylene glycol monobutyl ether
[0062] BTA: benzotriazole
[0063] HAS: hydroxylammonium sulfate
2 TABLE 2 Comparative Example 1 example 1 Treating condition:
temperature (.degree. C.) 70 70 time (minute) 10 10 Result:
releasing property .circleincircle. .DELTA. corrosion property
.circleincircle. .circleincircle.
[0064]
3 TABLE 3 Example 2 Example 3 Compound of the formula part by
weight 6.0 6.0 (I): A Water part by weight 23.0 24.0 Water-soluble
organic part by weight 12.5 23.0 solvent: THFA DMSO part by weight
7.5 5.0 Organic amines: MEA part by weight 25.0 25.0 Additive:
catechol part by weight 2.0 2.0 BTA part by weight 1.0 -- HAS part
by weight 23.0 15.0
[0065] A: 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone
[0066] MEA: monoethanolamine
[0067] THFA: tetrahydro furfuryl alchol
[0068] DMSO: dimethylsulfoxide
[0069] BTA: benzotriazole
[0070] HAS: hydroxylammonium sulfate
4 TABLE 4 Example 2 Example 3 Treating condition: temperature
(.degree. C.) 70 70 time (minute) 15 15 Result: releasing property
.circleincircle. .circleincircle. corrosion property
.circleincircle. .circleincircle.
[0071] The remover composition of the present invention is
excellent in an ability of removing a photoresist and a residue
generated in dry etching treatment, and manifest extremely low
corrosion property of materials such as an insulation film, metal
film and the like constituting a semiconductor element, therefore,
is suitably used in a process of washing semiconductor elements
such as an LSI element, liquid crystal panel element and the
like.
* * * * *